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DIM360 - Ver 2.8 (28 Apr 1998) 2100000/0
0458485
EUROPEAN PATENT SPECIFICATION
B1
19980729
EP
91304075.4
19910507
19921102
19961016
en
en
en
125149/90
19900515
JP
19980729
199831
19911127
199148
19980729
199831
19971105
6
6G 03F 7/039 A
de
Bildaufbauschicht
en
Image forming layer
fr
Couche génératrice d'image
EP-A- 343 246
EP-A- 380 007
DE-A- 3 825 738
Kawamura, Kouichi, c/o Fuji Photo Film Co., Ltd.
4000 Kawashiri, Yoshida-cho
Haibara-gun, Shizuoka-ken
JP
Maemoto, Kazuo, c/o Fuji Photo Film Co., Ltd.
4000 Kawashiri, Yoshida-cho
Haibara-gun, Shizuoka-ken
JP
Fuji Photo Film Co., Ltd.
00202402
JHB/OP-90117
210 Nakanuma Minamiashigara-shi
Kanagawa-ken
JP
Blake, John Henry Francis
et al
00028371
Brookes & Martin High Holborn House 52/54 High Holborn
London WC1V 6SE
GB
DE
GB
19921021
199243

BACKGROUND OF THE INVENTION

Field of the Invention
The present invention relates to a novel image forming layer, and more precisely it relates to an image forming layer enabling to obtain a negative image with high sensitivity from original image by light exposure.

Prior Arts
Recently, the development process in the formation of printing plates or resists has been carried out by the alkali development using an aqueous alkaline solution instead of the former development using a developer mainly consisting of an organic solvent from the viewpoints of the environmental safety and sanitary. Accordingly, it has been required to use a light-sensitive layer suitable for the alkali development, and various binder polymers or resins containing carboxyl groups are utilized. However, such binder compounds have serious drawbacks that when they are used in printing plates or resists the image portions obtained after the light exposure and the development tend to swell with the alkaline developer due to the carboxylic acid remained therein to unacceptably reduce the coating strength and the adhesion to the substrate of the image portions.
In order to eliminate those drawbacks, it was proposed to eliminate the carboxylic acid by decarbonation of the carboxylic acid by means of light exposure as disclosed in JP (KOKAI) No. 64-32255. However, this method enables to obtain only low sensitivity, and the image portions obtained with a weak light exposure in this method show poor scratch resistance during the development process since a lot of carboxylic acid remains in the image portions when the light exposure is rather weak.

SUMMARY OF THE INVENTION
Therefore, the object of the invention is to provide a image forming layer showing high sensitivity and excellent scratch resistance during the development process and free from the aforementioned drawbacks.
We have conducted various studies to achieve the foregoing object and finally found that it can be achieved by an image forming layer comprising a polymer introduced into a single molecule thereof with a component showing UV absorption at 320 nm or higher and a component containing a carboxylic acid (carboxylate) residue represented by the following general formula I.
Therefore, the present invention provides an image forming layer comprising a polymer which has a component showing UV absorption at 320 nm or higher (sensitizer moiety) selected from an aromatic ketone, aromatic thioketone, aromatic nitro compound, aromatic hydrocarbons, triarylpyrazoline, xanthene compound, cumarin compound, triphenylmethane compound and quinazolinone compound, and a component containing the carboxylic acid (carboxylate) group (carbonyl group-containing moiety) represented by the following general formula I:
-(Y)_l -X-(CH_2)_k -COOT (I)
wherein X represents sulphur, oxygen, single bond, C=W or N-U where W represents oxygen or sulphur and U represents an optionally substituted aryl, alkyl group or hydrogen, Y represents an optionally substituted alkylene, arylene, aralkylene group or divalent heterocyclic ring, and T represents a hydrogen. alkali metal. alkaline earth metal or HN(R^1) (R^2) (R^3) where R^1, R^2 and R^3, which may be identical or different. independently represent a hydrogen atom, optionally substituted alkyl or aryl group and R^1, R^2 and R^3 may join together to form a ring structure, the optional substituents of the groups U, Y, R^1, R^2, R^3 being selected from halogen atoms, cyano, nitro, hydroxyl, carboxyl groups, -OR, -COOR, -OCOR, -CONHR, -NHCOR where R represents an alkyl group containing 1 to 20 carbon atoms or aryl group containing 6 to 20 carbon atoms, aryl group as the substituent of the alkyl group and alkyl group as the substituent of the aryl group, k represents 0 or 1 and l is 0 or 1, provided that X represents C=W when k is 0.

DETAILED EXPLANATION OF THE INVENTION
The present invention will be described in more detail hereunder.
The polymer used in the present invention is introduced with the moiety containing the carboxyl group which may be decarbonated by light exposure and is represented by the above-mentioned general formula I (referred to as a "carboxyl group-containing moiety" hereinafter) and the moiety showing UV absorption at 320 nm or higher (referred to as a "sensitizer moiety" hereinafter).
In the general formula I, U preferably represents an aryl group containing 6 to 20 carbon atoms such as phenyl and naphthyl or an alkyl group containing 1 to 20 carbon atoms.
The substituents of those aryl and alkyl groups are selected from a halogen atom such as fluorine, chlorine, bromine and iodine atoms, cyano, nitro, hydroxyl, carboxyl groups, -OR, -COOR, -OCOR, -CONHR, -NHCOR where R represents an alkyl group containing 1 to 20 carbon atoms or aryl group containing 6 to 20 carbon atoms, aryl group as the substituent of the alkyl group and alkyl group as the substituent of the aryl group. As to the group Y, the alkylene group preferably contains 1 to 20 carbon atoms, the arylene group preferably contains 6 to 20 carbon atoms and the aralkylene group preferably contains 7 to 20 carbon atoms, and the divalent heterocyclic ring group is preferably a divalent group derived from a carbazole, indole or pyrazole ring. Examples of the substituent of those alkylene, arylene, aralkylene and divalent heterocyclic ring are those mentioned above as the substituent of the group U.
Examples of the alkyl and aryl groups of R^1, R^2 and R^3 and the substituent thereof respectively are those mentioned as the group U and therefor.
Preferred examples of the carboxyl group-containing moiety include those having a residue or residues of indole-3-acetic acid, phenoxyacetic acid, 2-methylphenoxyacetic acid, 3-methoxyphenoxyacetic acid, 2-nitrophenoxyacetic acid, 3-chlorophenoxyacetic acid, 4-methylphenoxyacetic acid, n-butoxyacetic acid, thiophenoxyacetic acid, 3-methoxythiophenoxya cetic acid, 2-chlorothiophenoxyacetic acid, 2-methylthiophenoxya cetic acid, 4-nitrothiophenoxyacetic acid, n-butylthioacetic acid, phenylacetic acid, 2-nitrophenylacetic acid, 4-nitrophenylacetic acid, 2,4-dinitrophenylacetic acid, benzoylformic acid, 4-chlorobenzoylformic acid, thiobenzoylformic acid, pyruvic acid, N-phenylglycine, N-(3-chlorophenyl)glycine, N-(2,4-dichlorophenyl)glycine, N-(4-acetylphenyl)glycine, N-(2-nitrophenyl)glycine, N-(2,4-dinitrophnenyl)glycine, N-(4-cyanophenyl)glycine, N-(2-bromophenyl)glycine, N-(2-methylphenyl)glycine, N-(2-methoxyphenyl)glycine, N-(2,4-dimethoxyphenyl)glycine, N-(n-butylphenyl)glycine, N-methyl-N-(2-methylphenyl)glycine, N-methyl-N-(2-chlorophenyl)glycine, N-methyl-N-(2-nitrophenyl)glycine, N-methyl-N-(2-methoxyphenyl) glycine, N-(4 -carbamoylphenyl)glycine and N-(4-sulfamoylphenyl) glycine. The carboxyl group-containing moiety may be used in any combination of two or more different types thereof.
The carboxylic acid residue may be a carboxylate, i.e., a carboxylic acid salt residue. The carboxylic acid salt may be an alkali metal salt, alkaline earth metal salt or ammonium salt. Examples of the ammonium salt include those formed with an amine such as mono-, di- or trimethylamine, mono-, di- or triethylamine, mono-, di- or triisopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, N,N-diethylaniline and N,N-dimethylaniline.
The portion of -X-(CH_2)_k -COOT of the carboxyl group-containing moiety, when X represents sulfur, oxygen, single bond or N-U, is preferably bonded onto an aryl ring or aromatic heterocyclic ring from the viewpoint of the sensitivity of the layer.
The sensitizer moiety of the polymer according to the invention contains a residue or residues of compounds selected from the following : aromatic ketone compounds such as xanthone, fluorenone, benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, acetophenone, naphthylacetone, 4,4'-bisdimethylaminobenzophenone, trinitrofluorenone, dibenzosuberone, 2,5-bis-(4'-diethylaminobenzal)cyclopentanone, α , α -dichloro-4-phenoxyacetophenone, 1-hydroxycyclohexylphenylketone; aromatic thioketone compounds such as 4,4'-bisdimethylaminothiobenzophenone; quinone compounds such as benzoquinone, dichlorobenzoquinone, tetrachlorobenzoquinone, dichloronaphthoquinone, anthraquinone, phenanthrenequinone, dichloroanthraquinone, dinitroanthraquinone, alizarin and benzanthraquinone; aromatic nitro compounds such as nitrobenzene, 1-nitronaphthalene, 4-nitrobiphenyl, 4-nitrotoluene, 1,3-dinitrobenzene and 2,4,6-trinitroaniline; aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, benzanthracene and benzpyrene; triarylpyrazoline such as triphenylpyrazoline; monoimidazole compounds such as tetraphenylimidazole and triphenylimidazole; xanthene compounds such as Fluoresceine, Eosine Y, Rose Bengal, Erythrosine B and Phloxine; acridine compounds such as acriflavin, riboflavin, acridine, 9-phenylacridine, N-phenylacridine, phenazine, 2,3-diphenylquinoxaline and acenaphtho- [1,2 -b] -quinoxaline; cumarin compounds disclosed in USP No. 4,289,844 such as 7-N,N-diethylaminoketocumarin, 3-benzoyl-7-diethylaminocumarin, 3-benzoyl-7-methoxycumarin and 3,3'-carbonyl-bis(7-diethylaminocumarin); triphenylmethane compounds such as Thymol Blue, Bromothymol Blue and Bromocresol Green; quinazolinone compounds such as 2-methyl-3-benzenesulfonyloxy-4(3H)-quinazolinone and 2-(β -styryl-3-benzenesulfonyloxy-4(3H)-quinazolinone. The sensitizer moiety mentioned above may be used in any combination of two or more different types thereof.
The sensitizer moiety preferably shows absorption within a wave length range matching the wave length of the light source to be used.
The carboxyl group-containing moiety and the sensitizer moiety are bonded to the polymer main chaine directly or via a bridging group. The bridging group may be ether bond, amide bond, ester bond, urethane bond, ureide bond or those groups containing such bonds. Further, a part of the carboxyl group-containing moiety or the sensitizer moiety may be contained in the polymer main chain.
Examples of the bridging group containing ether bond, amide bond, ester bond, urethane bond and/or ureide bond include those represented by the following general formulae II, III, IV and V:
-L-(-R-L-)_n -R- (II)
-L-(-R-L-)_n - (III)
-R-(-L-R-)_n -L- (IV)
-R-(-L-R-)_n - (V)
wherein R, which may be identical or different, independently represents an alkylene, arylene, aralkylene group or a divalent heterocyclic ring; L, which may be identical or different, independently represents an ehter bond, amide bond, ester bond, urethane bond or ureide bond; and n is 0, 1 or 2.
Examples of the polymer used in the present invention include acrylic resin, vinyl polymerization resin including vinyl alcohol resin, polyurethane resin, polyurea resin, polyvinyl acetal resin, polyamide resin and epoxy resin. Among those resins, the vinyl polymerization resin is particularly preferred from the viewpoint of the facility of the synthesis thereof.
The polymer having the aforementioned carboxyl group-containing moiety and the sensitizer moiety may be obtained, for example, when the polymer is a vinyl polymerization resin, by copolymerizing a monomer or monomers having the carboxyl group-containing moiety of the following general formula VI;
CH_2=C(E)-Z -(Y)_l -(CH_2)_k -COOT (VI)
wherein E represents CH_3 or hydrogen atom and Z represents a bridging group such as an alkylene, arylene, aralkylene group, ether bond, amide bond, ester bond, urethane bond and a group consisting of two or more of those groups and bonds, and X, Y, T, l and k have the same meanings as defined in the aforementioned general formula I, with a monomer or monomers having the sensitizer moiety and polymerizable ethylenically unsaturated bond, and optionally with a monomer or monomers copolymerizable with those essntial monomers, for example, acrylic acid ester and methacrylic acid ester.
The polymer according to the invention may be either of a block copolymer, random copolymer or graft copolymer.
The carboxyl group-containing moiety and the sensitizer moiety may be also introduced into the polymer by a polymer reaction of vinyl polymer.
The monomer having the sensitizer moiety and an ethylenically unsaturated bond includes those represented by the following general formula, but it is not limited in them;
CH_2=C(E)-Z-S
wherein E and Z have the same meanings as defined in the general formula VI and S represents the sensitizer moiety.
Examples of this monomer include those exemplified below,
The monomer optionally copolymerized in the polymer according to the invention is selected from, for example, compounds having an addition polymerizable unsaturated bond including acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, vinyl ethers, vinyl esters, styrene derivatives and crotonic acid esters. Examples of this monomer include acrylic acid esters such as alkyl acrylate, preferably C_{1-10} alkyl acrylate, e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate aryl acrylate, e.g., phenyl acrylate; methacrylic acid esters such as alkyl methacrylate, preferably C_{1-10} alkyl methacrylate, e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate and tetrahydrofurfuryl methacrylate and aryl methacrylate, e.g., phenyl methacrylate, cresyl methacrylate and naphthyl methacrylate; acrylamides such as acrylamide, N-alkylacrylamide preferably comprising a C_{1-10} alkyl group, e.g., methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl and hydroxyethyl, N-arylacrylamide comprising an aryl group such as phenyl, tolyl, nitrophenyl, naphthyl and hydroxyphenyl, N,N-dialkylacrylamide preferably comprising C_{1-10} alkyl groups, e.g., methyl, ethyl, butyl, i-butyl, ethylhexyl and cyclohexyl, N,N-diarylacrylamide comprising aryl groups such as phenyl, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide; methacrylamide such as methacrylamide, N-alkylmethacrylamide preferably comprising a C_{1-10} alkyl group, e.g., methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl and cyclohexyl, N-arylmethacrylamide comprising an aryl group such as phenyl, N,N-dialkylmethacrylamide preferably comprising C_{1-10} alkyl groups such as ethyl, propyl and butyl, N, N-diarylmethacrylamide comprising aryl groups such as phenyl, N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide and N-ethyl-N-phenylmethacrylamide; allyl compounds including allyl esters such as allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate, and allyloxyethanol; vinyl ethers including alkyl vinyl ether such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether and tetrahydrofurfuryl vinyl ether, vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; vinyl esters such as vinyl butyrate,vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl cyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate; styrene and derivatives thereof such as styrene, alkylstyrene, e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bytylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylsty rene, alkoxystyrenes, e.g., methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene, halogenostyrenes, e.g., chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene and 4-fluoro-3-trifluoromethylsty rene; crotonic acid esters including alkyl crotonate such as butyl crotonate, hexyl crotonate and glycerin monocrotonate; dialkyl itaconates such as dimethyl itaconate, diethyl itaconate and dibutyl itaconate; dialkyl maleates such as dimethyl maleate; dialkyl fumarates such as dibutyl fumarate; acrylonitrile, methacrylonitrile;and any combination of those monomers.
When the polymer is consisted of urethane resin, it may be obtained by reacting a diol having the carboxyl group-containing moiety and represented by the following general formula VII;
(HOCH_2CH_2)_2 N-Z-(Y)_l -X-(CH_2) _k -COOT (VII)
wherein X, Y, T, l and k have the same meanings as defined hereinbefore and Z represents a bridging group including a single bond, and a diol having the sensitizer moiety and represented by the following genaral formula VIII;
(HOCH_2CH_2)_2 N-Z-S (VIII)
wherein Z represents a bridging group including a single bond and S represents a sensitizer moiety, with a diisocyanate.
When the polymer is consisted of polyester resin, it may be obtained by reacting the diols of the formulae VII and VIII above with a compound having acid chloride functionals at the both terminals thereof.
The acid content of the polymer according to the invention is preferably from 6.0 meq/g to 0.01 meq/g, particularly from 3.0 meq/g to 0.1 meq/g. When the acid content is lower than 0.01 meq/g, the developability with alkaline developper is unacceptably deteriorated, whereas when it exceeds 6.0 meq/g, the coating strength and the adhesion to the substrate are unacceptably lowered. The polymer may additionally contain carboxyl residues which cannot be decarbonated by light exposure. Further, two or more different types of the carboxyl group-containing moiety which can be decarbonated by light exposure may be contained in a sigle molecule of the polymer.
The weight average molecular weight of the polymer according to the present invention, determined by the gel permeation chromatography, is preferably from 2,000 to 1,000,000, particularly from 8,000 to 200,000. When it is lower than the above-specified range, the scratch resistance of the image portions is unacceptably deteriorated, while the developability is deteriorated when it exceeds the range.
It is possible to use the polymer in a combination of two or more different types of the polymer.
Further, it is also possible to use the polymer mixed with other polymers which do not have the carboxyl group-containing moiety and/or the sensitizer moiety. In this case, such optional polymer should constitute less than 95 weight % of the whole image forming layer, since the intended advantage of the present invention cannot be obtained when the weight ratio of the optional polymer exceeds the above-identified upper limit. Examples of the optional polymer which may be contained in the image forming layer according to the invention include polyamide resin, epoxy resin, polyurethane resin, acryl resin, polyester resin, or polyvinyl acetal resin.
The molar ratio of the carboxyl group-containing moiety to the sensitizer moiety in the polymer used in the present invention is preferably not less than 0.1, particularly not less than 0.5.
When the polymer is a vinyl polymerizarion resin, it preferably comprises 0.5 to 95 mole % of the carboxyl group-containing monomer and 0.5 to 50 mole % of the monomer containing the sensitizer moiety.
The image forming layer according to the present invention may contain a diazonium compound. Examples of the diazonium compound are those disclosed in USP Nos. 3,867,147 and 2,632,703 and particularly preferred are diazo resins such as a condensate of an aromatic diazonium salt and an active carbonyl group-containing compound such as formaldehyde. Preferred examples of the diazo resin are hexafluorophosphate, tetrafluorophosphate and phosphate of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde. In addition, the preferred examples further include sulfonates such as p-toluenesulfonate and 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate, phosphinates such as benzenephosphinate, salts with hydroxyl group-containing organic compounds such as salt with 2,4-dihydroxybenzophenone and organic carboxylates of a condensate of p-diazodiphenylamine and formaldehyde as disclosed in USP No. 3,300,309. Moreover, those obtained by condensing 3-methoxy-4-diazodiphenylamine with 4,4'-bismethoxymethyldiphenyl ether and then converted to a mesitylenesulfonate salt as disclosed in JP (KOKAI) No. 58-27141 are also suitable. Further, also preferred are the diazonium salt compounds having an alkali soluble group disclosed in JP (KOKAI) Nos. 1-102457, 1-254949, 2-66, 2-29650 and 1-245246.
Those diazonium compounds may be added to the image layer in an amount of from 0.1 to 50 % by weight, preferably 3 to 15 % by weight of the whole image forming layer. When the amount is lower than 1 % by weight, the affinity to the substrate is not satisfactorily improved, whereas the amount exceeds 50 % by weight, the properties of the coating is deteriorated.
The image forming layer according to the present invention may further contain a dye compound. Preferred examples of the dye compound include oil-soluble dyes such as C.I. 26105 (Oil Red RR), C.I. 21260 (Oil Scarlet #308), C.I. 74350 (Oil Blue), C. 1. 52015 (Methylene Blue), C.I. 42555 (Crystal Violet) and C.I. 42595 (Victoria Pure Blue).
Those dyes may be preferably added into the image forming layer of the invention in an amount of 0.01 to 20.0 % by weight of the whole image forming layer.
The image forming layer according to the invention may also contain the low molecular sensitizers disclosed in JP (KOKAI) No. 64-32255.
The image forming layer according to the invention may also contain a polymerizable compound having an ethylenically unsaturated bond, i.e., a compound having at least one ethylenically unsaturated bond in the chemical structure of the molecule thereof, which includes monomer and prepolymer, i.e., oligomer such as dimer, trimer and other oligomer, a mixture thereof and a copolymer thereof. Examples of such compound include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and polyfunctional aliphatic alcohol compounds, amides of unsaturated carboxylic acid and aliphatic polyamine compounds.
Examples of the unsaturated caboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid.
Examples of the salt of the unsaturated carboxylic acid include alkali metal salts such as sodium salt and potassium salt of the aforementioned acid.
Examples of the ester of the polyfunctional aliphatic alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerithritol diacrylate, pentaerithritol triacrylate, pentaerithritol tetraacrylate, dipentaerithritol diacrylate, dipentaerithritol triacrylate, dipentaerithritol tetraacrylate, dipentaerithritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, polyester acrylate oligomer; methacrylic acid esters such as tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerithritol dimethacrylate, pentaerithritol trimethacrylate, dipentaerithritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-(3-p-(methacryloxy-2-hydroxypropoxy)phenyl)dimethylmethane, bis-(p-(methacryloxyethox-y)phenyl)dimethylmethane ; itaconic acid esters such as ethylene glycol diitaconate, propylene glycol diitaconate, 1, 3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerithritol diitaconate, sorbitol tetraitaconate ; crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerithritol dicrotonate, sorbitol tetracrotonate ; isocrotonic acid esters such as ethylene glycol diisocrotonate, pentaerithritol diisocrotonate, sorbitol tetraisocrotonate, maleic acid esters such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerithritol dimaleate, sorbitol tetramaleate; and mixtures of aforementioned esters.
Examples of the amide of the aliphatic polyamine and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1, 6-hexamethylenebis-methacrylamide.
The polymerizable compound having an ethylenycally unsaturated bond encompasses the vinyl urethane compounds having two or more polymerizable vinyl groups in the single molecule thereof, which are disclosed in JP (KOKAI) No. 48-41708 and obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the single molecule thereof with a vinyl monomer represented by the following general formula IX;
CH_2=C(R)COOCH_2CH(R')OH (IX)
wherein R and R' independently represent H or CH_3.
Those polymerizable compounds having one or more ethylenycally unsaturated bonds may be preferably added into the image forming layer of the present invention in an amount of 1 to 80 weight %, particularly 5 to 60 % by weight of the whole image forming layer.
The light-sensitive composition according to the invention may contain, other than the components mentioned above, a pigment, stabilizer, filler, surfactant, plastisizer to improve the properties of the composition, if necessary.
The image forming layer of the present invention is formed by dissolving the light-sensitive composition in a solvent, applying the dissolved compostion on a suitable substrate and drying it. The application amount is preferably from 0.01 to 500 g/m^2, particularly from 0.1 to 200 g/m^2 in dry weight.
Examples of the solvent for dissolving the composition include methanol, ethanol, isopropanol, n-butanol, t-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethyl acetate, ethylene glycol, tetrahydrofuran, dioxane, dimethylsulfoxide, N, N-dimethylformamide, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-methoxy-2-acetoxypropane, 2-methoxy-1-acetoxypropane, ethyl acetate, methyl acetate, toluene, xylene and a mixture of those solvent.
Examples of the substrate to which the image forming layer of the invention is applied include paper; paper laminated with a plastic sheet such as a sheet of polyethylene, polypropylene or polystyrene; metal plates such as aluminum (inclusive of aluminum alloys), zinc and copper plates; films of plastics such as scellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetal; and paper or plastic films which are laminated with a foil of the foregoing metals or to which a layer of such a metal is deposited. Among these, an aluminum plate is particularly preferred because of its high dimentional stability and low cost. In addition, composite sheets comprising polyethylene terephthalate to which an aluminum sheet is coated as disclosed in JP-B (KOKOKU) No. 48-18327 are also preferred.
If the substrate has a metal surface, in particular an aluminum surface, it is desirable to subject it to a surface treatment, for example, an electrolytic graining treatment, combined graining treatment, graining treatment, immersion treatment into a solution of sodium silicate, potassium fluorozirconate, phosphates, anodization treatment. Preferred examples of the anodization treatment include the anodization in sulfuric acid with a high current density as disclosed in BP No. 1,412,768, the anodization in a phosphoric acid electrolytic bath as disclosed in USP No. 3,511,661 and the anodization in a mixed acid of phosphoric acid and sulfuric acid as disclosed in JP-B No. 46-43124, JP-A Nos. 52-103208 and 55-28400. Also preferred plated are an aluminum plate treated by immersing it into an aqueous solution of sodium silicate after the graining and the aluminum plate treated by immersing it into an aqueous solution of alkali metal silicate after the anodization as disclosed in JP-B No. 47-5125. The anodization treatments mentioned above are carried out by an electrolysis in an electrolyte comprisingone or more of aqueous or non-aqueous solutions of a inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid or an organic acid such as oxalic acid, sulfamic acid, salts thereof or a mxture thereof using the aluminium plate to be anodized as the anode.
Also preferred are those subjected to a sealing treatment after the graining treatment and the anodization. Such sealing treatment is carried out by immersing the plate into an aqueous solution of sodium silicate or polyvinylphosphonic acid, hot water, hot aqueous solution of an inorganic or organic salt or by steaming treatment.
The silicate electrodeposition disclosed in USP No. 3,658,662 may be also effectively used as the surface treatment.
The image forming layer of the present invention applied to the surface of the substrate is imagewise exposed to light through an original transparency carrying line or half-tone dot images and then developed with an aqueous developer to provide relief images negative with respect to the original.
As a light source used in the exposure, there may be named, for instance, a carbon arc lamp, a mercury lamp, a xenon lamp, tungsten lamp, metal halide lamp and argon laser.
Any known developer may be used for the development of the image forming layer according to the invention, but preferred are as follows.
Desirable developers comprise at least one alkaline agent and water as essential components.
Examples of the alkaline agent are inorganic alkaline agents such as sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium secondary phosphate, sodium tertiary phosphate, ammonium secondary phosphate, ammonium tertiary phosphate, sodium metasilicate, sodium carbonate, and aqueous ammonia; organic alkaline agents of amine compounds such as mono-, di- and trimethylamines, mono-, di- and triethylamines, mono-, di and triisopropylamines, n-butylamine, mono-, di and triethanolamines, mono-, di- and triisopropanolamines, ethyleneimine and ethylenediimine.
These alkaline agents are used in the developer in an amount of from 0.05 to 10 % by weight, preferably 0.5 to 5 % by weight. If the amount is less than 0.05 % by weight, the development is incomplete, whereas if it exceeds 10 % by weight, the images are likely to suffer scratches upon development.
The developer for developing the image forming layer of the present invention may optionally comprise specific organic solvents.
The organic solvents are preferably those capable of solubilizing or swelling the non-exposed areas (non-image areas) of the light-sensitive layer during the development and having a solubility in water of not more than 10 % by weight at room temperature (about 20 ° C). Examples of such organic solvent are carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, and butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methyl phenyl carbinol, n-amyl alcohol and methylamyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; and halogenated hydrocarbons such as methylene dichloride, ethylene dichloride and monochlorobenzene. Those organic solvents may be used alone or in any combination thereof. Among those solvents, particularly preferred are ethylene glycol monophenyl ether and benzyl alcohol. The organic solvents may be used in an amount of from 0 to 20 % by weight, preferably 2 to 10 % by weight of the developer to obtain a good result.
The developer may comprise water-soluble sulfites, preferably water-soluble sulfites of alkali or alkaline earth metals such as sodium, potassium, lithium and magnesium. The amount of the sulfite is 0 to 4 % by weight, preferably 0.1 to 1 % by weight of the developer.
It is also possible to use alkaline-soluble pyrazolone compounds, alkaline-soluble thiol compounds, hydroxyl group-containing aromatic compounds such as methyl resorcin in place of or in combination with the aforementioned water-soluble sulfite.
Moreover, to promote the dissolution of the foregoing organic solvent in water, specific solubilizing agents may be incorporated into the developer. The solubilizing agents are preferably those having a higher solubility in water and a lower molecular weight than those of the aforementioned organic solvents, for example, lower alcohols and ketones. Besides, anionic and amphoteric surfactants may also be used.
Preferred examples of such alcohols and ketones are methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-methoxy-4-methylbutanol and N-methylpyrrolidone. Preferred examples of the surfactant are sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, sodium N-methyl-N-pentadecylaminoacetate and sodium laurylsulfate. The amount of the solubilizing agent such as the alcohols and ketones is preferably not more than 30% by weight of the total weight of the developer.
The image forming layer according to the invention is mainly used as a material for printing plate and resist.
The image forming layer according to the invention shows an extremely high sensitivity and excellent scratch resistance of the image areas upon development.

EXAMPLES
The present invention will be further illustrated hereafter by means of the following specific examples, but it is not limited thereto. The term "%" in the examples means "% by weight unless otherwise specified".

Preparation of Polymer
The component monomers shown in Table 1 were dissolved in tetrahydrofuran (THF) in a ratio of 1 mol of the monomers to 300 ml of THF and heated up to 65 ° C under a nitrogen flow. Then, the monomer solution was added with azobisisobutyronitrile in a ratio of 1 g of azobisisobytyrinitrile to 1 mol of the monomers and stirred. After stirring for 10 hours, the polymerization liquor was poured into 10 l of water to deposit polymer. The deposited polymer was taken by filtration and dried.

Table 1
Polymer No. | Monomer (molar ratio) | Molecular Weight | Acid Content (meq/g)
| I | II | III | IV | |
1 | A (50) | S-6 (50) | | | 5000 | 1.62
2 | A (10) | S-6 (10) | P (80) | | 50000 | 0.70
3 | A ( 5) | S-6 ( 5) | Q (50) | T (40) | 120000 | 0.37
4 | A (10) | S-4 ( 5) | R (30) | W (55) | 12000 | 0.76
5 | A (40) | S-4 (50) | S (10) | | 30000 | 1.60
6 | A (30) | S-2 (30) | T (40) | | 80000 | 1.48
7 | A (40) | S-2 (20) | Q (40) | | 10000 | 2.10
8 | B (50) | S-6 (50) | | | 8000 | 1.70
9 | B (30) | S-5 (10) | Q (60) | | 3000 | 1.78
10 | C (50) | S-6 (50) | | | 7000 | 1.44
11 | C (20) | S-4 (40) | U (40) | | 30000 | 0.90
12 | C (50) | S-4 (20) | V (30) | | 110000 | 1.91
13 | C ( 5) | S-2 ( 5) | V (40) | R (50) | 50000 | 1.53
14 | C ( 5) | | V (45) | R (50) | 250000 | 0.51
15 | A (50) | | Q (50) | | 40000 | 2.84

Monomer I: Monomer having carboxyl group-containing moiety

Monomer II: Monomer having sensitizer moiety
The symbols used in Table 1 correspond to those used in Pages 9 to 10 hereinbefore.

Monomers III and IV:
P
Methyl methacrylate
Q
Ethyl methacrylate
R
Acrylonitrile
S
Acrylic acid
T
2-Hydroxyethyl methacrylate
U
Ethyl acrylate
V
2-Hydroxyethyl acrylate
W
Butyl methacrylate

Examples 1 to 13
Each light-sensitive solution having the following composition was prepared, then coated on a polyethylene terephthalate sheet having a thickness of 25µ m by means of a rod coater and dried in an oven at 80 ° C for 2 minutes to form an image forming layer having a dry thickness of 10 µ m.
Light-sensitive solution
25 % Solution of Polymer No. 1 to 13 in THF | 2 g
2-Methoxyethanol | 5 g
Each image forming layer thus obtained was imagewise exposed to light from PS light (Fuji Photo Film Co., Ltd) at a distance of 1 m therefrom through a step wedge (Fuji Photo Film Co., Ltd) for 5 minutes and immersed in a developer having the following composition at room temperature for one minute, followed by rubbing the surface thereof with absorbent cotton lightly to remove the unexposed areas so as to obtain a light yellow image.
Developer
Sodium carbonate | 5 g
2-Methoxyethanol | 5 g
Sodium dodecylbenzenesulfonate | 10 g
Water | 1000 g
The results are shown in Table 2 below.

Comparative Examples 1 and 2
The procedures of Examples 1 to 13 were repeated except that the following light-sensitive solutions were employed to obtain light yellow images.
Light-sensitive solution
25% Solution of Polymer No. 14 or 15 in THF | 2 g
Phenazine | 0.1 g
2-Methoxyethanol | 5 g
The results of those Comparative Examples are also shown in Table 2.

Table 2
Example No. | Polymer No. | Solid Sensitivity (step) | Scratch Resistance upon Development
1 | 1 | 1 | Good
2 | 2 | 3 | Good
3 | 3 | 6 | Excellent
4 | 4 | 5 | Excellent
5 | 5 | 2 | Good
6 | 6 | 1 | Good
7 | 7 | 1 | Good
8 | 8 | 1 | Good
9 | 9 | 2 | Excellent
10 | 10 | 1 | Good
11 | 11 | 3 | Good
12 | 12 | 5 | Excellent
13 | 13 | 6 | Excellent
Comparative Example No. | | |
1 | 14 | Not more than 1 | Bad
2 | 15 | Not more than 1 | Bad
As seen from the rusults shown in Table 2, the image forming layers of the present invention show higher sensitivity and more excellent scratch resistance upon development as compared with the comparative image forming layers.

Examples 14 to 26
The surface of an aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mesh pumice stone and thereafter sufficiently washed with water. The plate was immersed in 10 % sodium hydroxide aqueous solution at 70 ° C for 60 second to etch the plate, followed by washing it with running water, neutralizing and wasing with 20 % nitric acid solution and then electrolytically graining the plate by the electrochemical graining method as disclosed in JP-A No. 53-67507, i.e., electrolytically graining the plate in 1 % aqueous sulfuric acid solution utilizing an alternating sine waved current of V _A = 12.7 V and V _C = 9.1 V so that the quantity of electricity at the anode time was 160 coulomb/dm^2. Subsequently, the aluminum plate was immersed in 30% aqueous sulfuric acid solution at 55 ° C for two minutes to desmut the plate and was anodized in 7 % aqueous sulfuric acid solution until the thickness of the resultant aluminum oxide layer was 2.0 g/m^2. Thereafter, the plate was immersed in 3 % aqueous sodium silicate solution maintained at 70 ° C for one minute, then washed with water and dried.
Each light-sensitive solution having the following composition was applied on the above-obtained plate by means of a whirler and dried at 80 ° C for 2 minutes. The coated amount was 2.0 g/m^2 in dry weight.
Light-sensitive solution
25 % Solution of Polymer No. 1 to 13 in THF | 2 g
Victoria Pure Blue BOH | 0.018 g
2-Methoxyethanol | 8.5 g
Each image forming layer thus obtained was imagewise exposed to light from PS light (Fuji Photo Film Co., Ltd) at a distance of 1 m therefrom through a step wedge (Fuji Photo Film Co., Ltd) for 10 minutes and immersed in a developer having the following composition at room temperature for one minute, followed by rubbing the surface thereof with absorbent cotton lightly to remove the unexposed areas so as to obtain a light blue image.
Developer
Sodium sulfite | 5 g
Benzyl alcohol | 30 g
Sodium carbonate | 5 g
Sodium isopropylnaphthalenesulfonate | 12 g
Water | 1000 g
The results are shown in Table 3 below.

Comparative Examples 3 and 4
The procedures of Examples 14 to 26 were repeated except that the following light-sensitive solutions were employed to obtain printing plates having a light blue image.
Light-sensitive solution
25 % Solution of Polymer No. 14 or 15 in THF | 2 g
Victoria Pure Blue BOH | 0.018 g
Phenazine | 0.2 g
2-Methoxyethanol | 8.5 g
The results of those Comparative Examples are also shown in Table 3.

Table 3
Example No. | Polymer No. | Solid Sensitivity (step) | Scratch Resistance upon Development
14 | 1 | 1 | Good
15 | 2 | 4 | Good
16 | 3 | 8 | Excellent
17 | 4 | 7 | Excellent
18 | 5 | 2 | Good
19 | 6 | 3 | Good
20 | 7 | 2 | Good
21 | 8 | 1 | Good
22 | 9 | 3 | Excellent
23 | 10 | 2 | Excellent
24 | 11 | 2 | Good
25 | 12 | 4 | Excellent
26 | 13 | 7 | Excellent
Comparative Example No. | | |
3 | 14 | Not more than 1 | Bad
4 | 15 | Not more than 1 | Bad
As seen from the rusults shown in Table 3, the image forming layers of the present invention show higher sensitivity and more excellent scratch resistance upon development as compared with the comparative image forming layers.

Examples 27 to 39
The surface of an aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mesh pumice stone and thereafter sufficiently washed with water. The plate was immersed in 10 % sodium hydride aqueous solution at 70 ° C for 60 second to etch the plate, followed by washing it with running water, neutralizing and wasing with 20 % nitric acid solution and then electrolytically graining the plate by the electrochemical graining method as disclosed in JP-A No. 53-67507, i.e., electrolytically graining the plate in 1 % aqueous sulfuric acid solution utilizing an alternating sine waved current of V _A = 12.7 V and V _C = 9.1 V so that the quantity of electricity at the anode time was 160 coulomb/dm^2. Subsequently, the aluminum plate was immersed in 30 % aqueous sulfuric acid solution at 55 ° C for two minutes to desmut the plate and was anodized in 7 % aqueous sulfuric acid solution until the thickness of the resultant aluminum oxide layer was 2.0 g/m^2. Thereafter, the plate was immersed in 3 % aqueous sodium silicate solution maintained at 70 ° C for one minute, then washed with water and dried.
Each light-sensitive solution having the following composition was applied on the above-obtained plate by means of a whirler and dried at 80 ° C for 2 minutes. The coated amount was 2.0 g/m^2 in dry weight.
Light-sensitive solution
25 % Solution of Polymer No. 1 to 13 in THF | 2 g
Victoria Pure Blue BOH | 0.018 g
Tetrahydrofuran | 10 g
PF_6 salt of condensate of 4-diazodiphenylamine and formalin | 0.05 g
Each image forming layer thus obtained was imagewise exposed to light from PS light (Fuji Photo Film Co., Ltd) at a distance of 1 m therefrom through a step wedge (Fuji Photo Film Co., Ltd) for 5 minutes and immersed in a developer having the following composition at room temperature for one minute, followed by rubbing the surface thereof with absorbent cotton lightly to remove the unexposed areas so as to obtain a light blue image.
Developer
Sodium sulfite | 5 g
Benzyl alcohol | 30 g
Sodium carbonate | 5 g
Sodium isopropylnaphthalenesulfonate | 12 g
Water | 1000 g
The results are shown in Table 4 below.

Comparative Examples 5 and 6
The procedures of Examples 27 to 39 were repeated except that the following light-sensitive solutions containing the polymer No. 14 or 15 were employed to obtain printing plates having a light blue image.
Light-sensitive solution
25 % Solution of Polymer No. 14 or 15 in THF | 2 g
Victoria Pure Blue BOH | 0.018 g
Phenazine | 0.2 g
PF_6 salt of condensate of 4-diazodiphenylamine and formalin | 0.05 g
Tetrahydrofuran | 10 g
The results of those Comparative Examples are also shown in Table 4.

Table 4
Example No. | Polymer No. | Solid Sensitivity (step) | Scratch Resistance upon Development
27 | 1 | 2 | Excellent
28 | 2 | 4 | Excellent
29 | 3 | 8 | Excellent
30 | 4 | 6 | Excellent
31 | 5 | 2 | Excellent
32 | 6 | 3 | Excellent
33 | 7 | 2 | Excellent
34 | 8 | 1 | Excellent
35 | 9 | 4 | Excellent
36 | 10 | 3 | Excellent
37 | 11 | 3 | Excellent
38 | 12 | 4 | Excellent
39 | 13 | 7 | Excellent
Comparative Example No. | | |
5 | 14 | 1 | Slightly bad
6 | 15 | 1 | Slightly bad
As seen from the rusults shown in Table 4, the image forming layers of the present invention show higher sensitivity and more excellent scratch resistance upon development as compared with the comparative image forming layers.

Examples 40 to 52
Light-sensitive compositions having the following compositions were prepared, then applied on polyethylene terephthalate films having a thickness of 25 µ m by means of a rod coater so as to obtain a dry thickness of 50 µ m and dried in an oven at 100 ° C for 5 minutes.
Light-sensitive solution
25 % Solution of Polymer No. 1 to 13 in THF | 60 g
2,4-Dimethylthioxanthone | 0.3 g
Ethyl p-dimethylaminobenzoate | 0.33 g
Tribromomethylphenyl sulphone | 0.4 g
Trimethylolpropane triacrylate | 3.0 g
Trimethylolpropane diacrylate | 5.0 g
Tetraethylene glycol diacrylate | 2.0 g
Leucomethyl Violet | 0.08 g
1-Phenyl-3-morpholinomethyl-1,3,4-triazole-2-thione | 0.09 g
Victoria Pure Blue BOH | 0.01 g
Methyl cellosolve | 10 g
On the smoothened and dried copper surface of a copper-clad laminate, the light-sensitive solution was coated by means of a laminater Type A-24 (Du Pont) at 120 ° C. The image forming layer thus formed was exposed to light from Jet Light (2kW ultra high pressure mercury lamp, Oak Co., Ltd.) through a wiring pattern of a high contrast transparency where transparent areas of conductive pattern (line width: 100 µ m) were formed on the opaque background. After peeling off the polyethylene terephthalate film, the unexposed areas were removed by spraying 1 % aqueous solution of sodium carbonate to the surface at 40 ° C with a pressure of 1.5 kg/cm^2 for 60 seconds. The obtained resist images were evaluated.
The results are shown in Table 5.

Comparative Examples 7 and 8
The procedures of Examples 40 to 52 were repeated except that the following light-sensitive solution containing Polymer No. 14 or 15 to obtain resist images.
Light-sensitive solution
25 % Solution of Polymer No. 14 or 15 in THF | 60 g
2,4-Dimethylthioxanthone | 0.3 g
Ethyl p-dimethylaminobenzoate | 0.33 g
Tribromomethylphenyl sulphone | 0.4 g
Trimethylolpropane triacrylate | 3.0 g
Trimethylolpropane diacrylate | 5.0 g
Tetraethylene glycol diacrylate | 2.0 g
Leucomethyl Violet | 0.08 g
1-phenyl-3-morpholinomethyl-1,3,4-triazole-2-thione | 0.09 g
Victoria Pure Blue BOH | 0.01 g
Phenazine | 6 g
Methyl cellosolve | 10 g
The results of those Comparative Examples are also shown in Table 5.

Table 5
Example No. | Polymer No. | Quality of Resist Image
40 | 1 | Excellent
41 | 2 | Good
42 | 3 | Good
43 | 4 | Excellent
44 | 5 | Excellent
45 | 6 | Good
46 | 7 | Good
47 | 8 | Excellent
48 | 9 | Good
49 | 10 | Excellent
50 | 11 | Excellent
51 | 12 | Good
52 | 13 | Good
Comparative Example No. | |
7 | 14 | Fairly bad
8 | 15 | Fairly bad
As seen from the results shown in Table 5, the quality of the resist images obtained with the image forming layer of the present invention is more excellent than that obtained in Comparative Examples.

Examples 53 to 65
Light-sensitive solutions of the following composition comprising each of Polymers Nos. 1 to 13 were filtered through a microfilter of 0.2 µ m to prepare photoresist compositions. Each photoresist composition was applied to a silicon wafer and dried in a convection oven at 90° C for 30 minutes to obtain a resist film of a thickness of 1.5 µ m. The resist film was exposured by means of a reduced projection exposure device, then developed with the following developer, rinsed with water for 30 seconds and dried.
Light-sensitive solution
Polymer No. 1 to 13 | 5 g
Ethyl lactate | 15 g
Developer
Benzyl alcohol | 15 g
Sodium carbonate | 5 g
Sodium isopropylnaphthalenesulfonate | 12 g
Water | 1000 g
All of the resist images were obtained with excellent quality.

Comparative Examples 9 and 10
The procedures of Examples 53 to 65 were repeated except that the following light-sensitive solution containing Polymer No. 14 or 15 to obtain resist images.
Light-sensitive solution
Polymer No. 14 or 15 | 5 g
Phenazine | 0.1 g
Ethyl lactate | 15 g
The qualities of the obtained images were bad.
1. An image forming layer comprising a polymer which has a component showing UV absorption at 320 nm or higher (sensitizer moiety) selected from an aromatic ketone, aromatic thioketone, aromatic nitro compound, aromatic hydrocarbons, triarylpyrazoline, xanthene compound, cumarin compound, triphenylmethane compound and quinazolinone compound, and a component containing the carboxylic acid (carboxylate) group (carbonyl group-containing moiety) represented by the following general formula I:
-(Y)_l -X- (CH_2)_k -COOT (I)
wherein X represents sulphur, oxygen,, single bond, C=W or N-U where W represents oxygen or sulphur and U represents an optionally substituted aryl, alkyl group or hydrogen, Y represents an optionally substituted alkylene, arylene, aralkylene group or divalent heterocyclic ring, and T represents a hydrogen, alkali metal, alkaline earth metal or HN(R^1) (R^2) (R^3) where R^1, R^2 and R^3, which may be identical or different, independently represent a hydrogen atom, optionally substituted alkyl or aryl group and R^1, R^2 and R^3 may join together to form a ring structure, the optional substituents of the groups U, Y, R^1, R^2, R^3 being selected from halogen atoms, cyano, nitro, hydroxyl, carboxyl groups, -OR, -COOR, -OCOR, -CONHR, -NHCOR where R represents an alkyl group containing 1 to 20 carbon atoms or aryl group containing 6 to 20 carbon atoms, aryl group as the substituent of the alkyl group and alkyl group as the substituent of the aryl group, k represents 0 or 1 and l is 0 or 1, provided that X represents C=W when k is 0.
2. The image forming layer according to claim 1, wherein X represents sulphur, oxygen or N-R where R represents hydrogen, phenyl or C_1 to C_{10} alkyl group.
3. The image forming layer according to claim 1, wherein Y represents an arylene group.
4. The image forming layer according to claim 1, wherein the carboxyl group-containing moiety and/or the sensitizer moiety are bonded to the polymer main chain via a bridging group selected from the group of ether bond, amide bond, ester bond, urethane bond, ureide bond or those groups containing such bonds.
5. The image forming layer according to claim 1, wherein the bridging group is selected from those represented by the following general formulae II, III, IV and V:
-L-(-R-L-)_n -R- (II)
-L-(-R-L-)_n - (III)
-R-(-L-R-)_n -L- (IV)
-R-(-L-R-)_n - (V)
wherein R, which may be identical or different, independently represents an alkylene, arylene, aralkylene group or a divalent heterocyclic ring; L, which may be identical or different, independently represents an ether bond, amide bond, ester bond, urethane bond or ureide bond; and n is 0,1 or 2.
6. The image forming layer according to claim 1, wherein the polymer is acrylic resin, vinyl polymerization resin, polyurethane resin, polyurea resin, polyvinyl acetal resin, polyamide resin or epoxy resin.
7. The image forming layer according to claim 1, wherein the acid content of the polymer is preferably from 6.0 meq/g to 0.01 meq/g, particularly from 3.0 meq/g to 0.1 meq/g.
8. The image forming layer according to claim 1, wherein the weight average molecular weight of the polymer, determined by the gel permeation chromatography, is preferably from 2,000 to 1,000,000, particularly from 8,000 to 200,000.
9. The image forming layer according to claim 1, wherein the polymer constitutes not less than 95% by weight of the whole image forming layer.
10. The image forming layer according to claim 1, wherein the molar ratio of the carboxyl group-containing moiety to the sensitizer moiety in the polymer is preferably not less than 0.1, particularly not less than 0.5.
11. The image forming layer according to claim 1, wherein, when the polymer is a vinyl polymerizarion resin, it preferably comprises 0.5 to 95 mole % of the monomer having the carboxyl group-containing monomer and 0.5 to 50 mole % of the monomer containing the sensitizer moiety.
12. The image forming layer according to claim 1, which contains a diazonium compound in an amount of from 0.1 to 50% by weight, preferably 3 to 15% by weight of the whole image forming layer.
13. The image forming layer according to claim 1, which contains a dye compound.
14. The image forming layer according to claim 1, which contains a polymerizable compound having an ethylenically unsaturated bond in an amount of 1 to 80% by weight, particularly 5 to 60% by weight of the whole image forming layer.
15. A process for the preparation of the polymer according to claim 1, comprising copolymerizing one or more monomers having the carboxyl group-containing moiety, one or more monomers having the sensitizer moiety and optionally other monomers copolymerizable with the aforementioned monomers.
16. The process according to claim 15, wherein one or more monomers having the carboxyl group-containing moiety represented by the following general formula VI;
CH_2 =C(E)-Z-(Y)_l -(CH_2)_k -COOT (VI)
wherein E represents CH_3 or hydrogen atom and Z represents a bridging group such as an alkylene, arylene, aralkylene group, ether bond, amide bond, ester bond, urethane bond and a group consisting of two or more of those groups and bonds, and X, Y, T, l and k having the same meanings as defined in the general formula I are copolymerized with one or more monomers having the sensitizer moiety represented by the following general formula;
CH_2 =C(E) -Z-S
wherein E and Z have the same meanings as defined in the general formula VI and S represents the sensitizer moiety and optionally one or more other monomers having an ethylenically unsaturated bond.
17. The process according to claim 15, wherein one or more monomers having the carboxyl group-containing moiety represented by the following general formula VII;
(HOCH_2 CH_2) -N-Z-(Y)_l -X-(CH_2)_k -COOT (VII)
wherein X, Y, T, l and k have the same meanings as defined in the general formula I and Z represents a bridging group including a single bond is copolymerized with one or more monomers having the sensitizer moiety is represented by the following general formula VIII;
(HOCH_2 CH_2) -N-Z-S (VIII)
wherein Z represents a bridging group including a single bond and S represents a sensitizer moiety.
18. The process according to claim 15, wherein one or more monomer having a carboxyl group-containing moiety of the formula VII and one or more monomers having the sensitizer moiety of the formula VIII are reacted with one or more compounds having acid chloride functionals at the both terminals thereof.
1. Bilderzeugungsschicht, die ein Polymer umfaßt, das aufweist eine Komponente mit einer UV-Absorption bei 320 nm oder höher (Sensibilisator-Rest), ausgewählt aus der Gruppe aromatisches Keton, aromatisches Thioketon, aromatische Nitroverbindung, aromatische Kohlenwasserstoffe, Triarylpyrazolin, Xanthen-Verbindung, Cumarin-Verbindung, Triphenylmethan-Verbindung und Chinazolinon-Verbindung, sowie eine Komponente, die eine Carbonsäure (Carboxylat)-Gruppe enthält (Carbonylgruppen-haltiger Rest), dargestellt durch die folgende allgemeine Formel (I):
-(Y)_l -X-(CH_2)_k-COOT (I)
worin bedeuten:
X Schwefel, Sauerstoff, eine Einfachbindung, C=W oder N-U, worin W für Sauerstoff oder Schwefel steht und U eine gegebenenfalls substituierte Aryl-, Alkyl-Gruppe oder Wasserstoff repräsentiert,
Y eine gegebenenfalls substituierte Alkylen-, Arylen-, Aralkylen-Gruppe oder einen divalenten heterocyclischen Ring und
T Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder HN(R^1)(R^2)(R^3), worin R^1, R^2 und R^3, die gleich oder verschieden sein können, unabhängig voneinander stehen für ein Wasserstoffatom, eine gegebenenfalls substituierte Alkyl- oder Arylgruppe und worin R^1, R^2 und R^3 miteinander verbunden sein können unter Bildung einer Ringstruktur,
wobei die gegebenenfalls vorhandenen Substituenten der Gruppen U, Y, R^1, R^2 und R^3 ausgewählt werden aus Halogenatomen, Cyano-, Nitro-, Hydroxyl-, Carboxyl-Gruppen, -OR, -COOR, -OCOR, -CONHR, -NHCOR, worin R steht für eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen oder eine Arylgruppe mit 6 bis 20 Kohlenstoffatomen, für eine Arylgruppe als Substituent der Alkylgruppe und für eine Alkylgruppe als Substituent der Arylgruppe,
k die Zahl 0 oder 1 und
l die Zahl 0 oder 1,
mit der Maßgabe, daß X für C=W steht, wenn k = 0.
2. Bilderzeugungsschicht nach Anspruch 1, worin X steht für Schwefel, Sauerstoff oder N-R worin R ein Wasserstoffatom, eine Phenyl- oder C_{1-10}-Alkylgruppe darstellt.
3. Bilderzeugungsschicht nach Anspruch 1, worin Y eine Arylengruppe darstellt.
4. Bilderzeugungsschicht nach Anspruch 1, worin der Carboxylgruppenenthaltende Rest und/oder der Sensibilisator-Rest über eine brückenbildende Gruppe, ausgewählt aus der Gruppe Etherbindung, Amidbindung, Esterbindung, Urethanbindung, Ureidbindung oder solchen Gruppen, die diese Bindungen enthalten, an die Polymer-Hauptkette gebunden ist (sind).
5. Bilderzeugungsschicht nach Anspruch 1, worin die brückenbildende Gruppe ausgewählt wird aus solchen der folgenden allgemeinen Formeln (II), (III), (IV) und (V):
-L-(-R-L-)_n -R- (II)
-L-(-R-L-)_n - (III)
-R-(-L-R-)_n -L- (IV)
-R-(-L-R-)_n - (V)
worin bedeuten:
R die gleich oder verschieden sein können, unabhängig voneinander eine Alkylen-, Arylen-, Aralkylen-Gruppe oder einen divalenten heterocyclischen Ring;
L die gleich oder verschieden sein können, unabhängig voneinander eine Etherbindung, eine Amidbindung, eine Esterbindung, eine Urethanbindung oder eine Ureidbindung; und
n die Zahl 0,1 oder 2.
6. Bilderzeugungsschicht nach Anspruch 1, worin das Polymer ein Acrylharz, Vinylpolymerisationsharz, Polyurethanharz, Polyharnstoffharz, Polyvinylacetalharz, Poylamidharz oder Epoxyharz ist.
7. Bilderzeugungsschicht nach Anspruch 1, worin der Säure-Gehalt des Polymers vorzugsweise 6,0 bis 0,01 meq/g, insbesondere 3,0 bis 0,1 meq/g, beträgt.
8. Bilderzeugungsschicht nach Anspruch 1, worin das gewichtsdurchschnittliche Molekulargewicht des Polymers, bestimmt durch Gelpermeationschromatographie, vorzugsweise 2000 bis 1 000 000, insbesondere 8000 bis 200 000, beträgt.
9. Bilderzeugungsschicht nach Anspruch 1, worin das Polymer nicht weniger als 95 Gew.-% der gesamten Bilderzeugungsschicht ausmacht.
10. Bilderzeugungsschicht nach Anspruch 1, worin das Molverhältnis zwischen dem Carboxylgruppen-enthaltenden Rest und dem Sensibilisator-Rest in dem Polymer vorzugsweise nicht weniger als 0,1, insbesondere nicht weniger als 0,5, beträgt.
11. Bilderzeugungsschicht nach Anspruch 1, worin dann, wenn das Polymer ein Vinylpolymerisationsharz ist, dieses vorzugsweise 0,5 bis 95 Mol-% des Monomers, das den Carboxylgruppen-haltigen Rest enthält, und 0,5 bis 50 Mol-% des Monomers, das den Sensibilisator-Rest enthält, umfaßt.
12. Bilderzeugungsschicht nach Anspruch 1, die eine Diazonium-Verbindung in einer Menge von 0,1 bis 50 Gew.-%, vorzugsweise von 3 bis 15 Gew.-%, bezogen auf die gesamte Bilderzeugungsschicht, enthält.
13. Bilderzeugungsschicht nach Anspruch 1, die eine Farbstoff-Verbindung enthält.
14. Bilderzeugungsschicht nach Anspruch 1, die eine polymerisierbare Verbindung mit einer ethylenisch ungesättigten Bindung in einer Menge von 1 bis 80 Gew.-%, insbesondere von 5 bis 60 Gew.-%, bezogen auf die gesamte Bilderzeugungsschicht, enthält.
15. Verfahren zur Herstellung des Polymers nach Anspruch 1, das umfaßt die Copolymerisation eines oder mehrerer Monomerer, die den Carboxylgruppen enthaltenden Rest aufweisen, eines oder mehrere Monomerer, die den Sensibilisator-Rest aufweisen, und gegebenenfalls anderer (weiterer) Monomerer, die mit den obengenannten Monomeren copolymerisierbar sind.
16. Verfahren nach Anspruch 15, worin ein oder mehr Monomere, die den Carboxylgruppen enthaltenden Rest aufweisen, dargestellt durch die folgende allgemeine Formel (Vl):
CH_2=C(E)-Z -(Y)_l -(CH_2)_k -COOT (VI)
worin bedeuten:
E CH_3 oder ein Wasserstoffatom und
Z eine brückenbildende Gruppe, beispielsweise eine Alkylen-, Arylen-, Aralkylen-Gruppe, eine Etherbindung, eine Amidbindung, eine Esterbindung, eine Urethanbindung und eine Gruppe, die aus zwei oder mehr dieser Gruppen und Bindungen besteht, und worin
X, Y, T, l und k die gleichen Bedeutungen haben wie sie in bezug auf die allgemeine Formel I angegebenen worden sind,
copolymerisiert werden mit einem oder mehreren Monomeren, die den Sensibilisator-Rest aufweisen, dargestellt durch die folgende allgemeine Formel:
CH_2=C(E)-Z-S
worin E und Z die gleichen Bedeutungen wie in bezug auf die allgemeine Formel (VI) definiert haben und S den Sensibilisator-Rest darstellt,
und gegebenenfalls mit einem oder mehreren anderen (weiteren) Monomeren, die eine ethylenisch ungesättigte Bindung aufweisen.
17. Verfahren nach Anspruch 15, worin ein oder mehrere Monomere, die den Carboxylgruppen enthaltenden Rest aufweisen, dargestellt durch die folgende allgemeine Formel (VII):
(HOCH_2CH_2) N-Z-(Y)_l -X-(CH_2)_k -COOT (VII)
worin X, Y, T, l und k die gleichen Bedeutungen wie in bezug auf die allgemeine Formel (I) definiert, haben und Z für eine brückenbildende Gruppe einschließlich einer Einfachbindung steht,
copolymerisiert wird (werden) mit einem oder mehreren Monomeren, die den Sensibilisator-Rest aufweisen, dargestellt durch die folgende allgemeine Formel (VIII):
(HOCH_2CH_2) N-Z-S (VIII)
worin Z eine brückenbildende Gruppe einschließlich einer Einfachbindung und S einen Sensibilisator-Rest darstellen.
18. Verfahren nach Anspruch 15, bei dem ein oder mehr Monomere, die einen Carboxylgruppen enthaltenden Rest aufweisen, der Formel (VII) und ein oder mehrere Monomere, die den Sensibilisator-Rest aufweisen, der Formel (VIII) mit einer oder mehr Verbindungen, die an ihren beiden Enden Säurechlorid-Funktionen aufweist (aufweisen), umgesetzt werden.
1. Couche formant une image comprenant un polymère qui présente un constituant présentant une absorption UV à 320 nm ou supérieure (moitié sensibilisateur) choisi parmi une cétone aromatique, une thiocétone aromatique, un composé nitro aromatique, des hydrocarbures aromatiques la triarylpyrazoline, un composé de xanthène, un composé de coumarine, un composé de triphénylméthane et un composé de quinazolinone et un constituant contenant le groupe (carboxylate) d'acide carboxylique (moitié contenant un groupe carbonyle) représenté par la formule générale I suivante :
-(Y)_l -X-(CH_2)_k -COOT (I)
dans laquelle X représente le soufre, l'oxygène, une liaison simple, C=W ou N-U, où W représente l'oxygène ou le soufre et U représente un groupe aryle, alkyle facultativement substitué ou l'hydrogène, Y représente un groupe alkylène, arylène, aralkylène facultativement substitué ou un noyau hétérocyclique divalent, et T représente l'hydrogène, un métal alcalin, un métal alcalino-terreux ou HN(R^1)(R^2)(R^3), où R^1, R^2 et R^3 qui peuvent être identiques ou différents représentent indépendamment un atome d'hydrogène, un groupe alkyle ou aryle facultativement substitué et R^1, R^2 et R^3 peuvent se joindre ensemble pour former une structure de noyau, les substituants facultatifs des groupes U, Y, R^1, R^2, R^3 étant choisis parmi des atomes d'halogène, les groupes cyano, nitro, hydroxyle, le carboxyle, -OR, -COOR, -OCOR, -CONHR, -NHCOR, où R représente un groupe alkyle contenant de 1 à 20 atomes de carbone ou un groupe aryle contenant de 6 à 20 atomes de carbone, un groupe aryle comme substituant du groupe alkyle et un groupe alkyle comme substituant du groupe aryle, k représente 0 ou 1 et l est égal à 0 ou à 1, à condition que X représente C=W lorsque k est égal à 0.
2. Couche formant une image selon la revendication 1, dans laquelle X représente le soufre, l'oxygène ou N-R, où R représente l'hydrogène, le groupe phényle ou un groupe alkyle en C_1-C_{10}.
3. Couche formant une image selon la revendication 1, dans laquelle Y représente un groupe arylène.
4. Couche formant une image selon la revendication 1, dans laquelle la moitié contenant un groupe carboxyle et/ou la moitié sensibilisateur sont liées à la chaîne principale du polymère via un groupe de pontage choisi parmi une liaison éther, une liaison amide, une liaison esther, une liaison uréthane, une liaison uréido ou des groupes contenant de telles liaisons.
5. Couche formant une image selon la revendication 1, dans laquelle le groupe de pontage est choisi parmi ceux représentés par les formules générales II, III, IV et V suivantes :
-L-(-R-L-)_n -R- (II)
-L-(-R-L-)_n - (III)
-R-(-L-R-)_n -L- (IV)
-R-(-L-R-)_n- (V)
dans lesquelles R, qui peut être identique ou différent, représente indépendamment un groupe alkylène, arylène, aralkylène ou un noyau hétérocyclique divalent; L, qui peut être identique ou différent, représente indépendamment une liaison éther, une liaison amide, une liaison ester, une liaison uréthane ou une liaison uréido; et n est égal à 0, 1 ou 2.
6. Couche formant une image selon la revendication 1, dans laquelle le polymère est une résine acrylique, une résine de polymérisation vinylique, une résine polyuréthane, une résine de polyurée, une résine d'acétal polyvinylique, une résine polyamide ou une résine époxy.
7. Couche formant une image selon la revendication 1, dans laquelle la teneur en acide du polymère est de préférence de 6,0 meq/g à 0,01 meq/g, particulièrement de 3,0 meq/g à 0,1 meq/g.
8. Couche formant une image selon la revendication 1, dans laquelle le poids moléculaire moyen en poids du polymère, déterminé par la chromatographie par perméation sur gel, est de préférence de 2 000 à 1 000 000, particulièrement de 8 000 à 200 000.
9. Couche formant une image selon la revendication 1, dans laquelle le polymère ne constitue pas moins de 95% en poids de la couche totale formant une image.
10. Couche formant une image selon la revendication 1, dans laquelle le rapport molaire de la moitié contenant un groupe carboxyle à la moitié sensibilisateur dans le polymère n'est de préférence pas inférieur à 0,1, particulièrement pas inférieur à 0,5.
11. Couche formant une image selon la revendication 1, dans laquelle lorsque le polymère est une résine de polymérisation vinylique il comprend de préférence de 0,5 à 95% en mole du monomère présentant le monomère contenant un groupe carboxyle et de 0,5 à à 50% en mole du monomère contenant la moitié sensibilisateur.
12. Couche formant une image selon la revendication 1, qui contient un composé de diazonium dans une quantité de 0,1 à 50% en poids, de préférence de 3 à 15% en poids de la couche totale formant une image.
13. Couche formant une image selon la revendication 1, qui contient un composé de colorant.
14. Couche formant une image selon la revendication 1, qui contient un composé polymérisable présentant une liaison éthyléniquement insaturée dans une quantité de 1 à 80% en poids, particulièrement de 5 à 60% en poids de la couche totale formant une image.
15. Procédé pour la préparation du copolymère selon la revendication 1, comprenant la copolymérisation d'un ou plusieurs monomères présentant la moitié contenant un groupe carboxyle, d'un ou plusieurs monomères présentant la moitié sensibilisateur et facultativement d'autres monomères copolymérisables avec les monomères cités précédemment.
16. Procédé selon la revendication 15, dans lequel un ou plusieurs monomères présentant la moitié contenant un groupe carboxyle représentée par la formule générale VI suivante :
CH_2= C(E)-Z-(Y)_l -(CH_2)_k -COOT (VI)
dans laquelle E représente CH_3 ou un atome d'hydrogène et Z représente un groupe de pontage, tel qu'un groupe alkylène, arylène, aralkylène, une liaison éther, une liaison amide, une liaison ester, une liaison uréthane et un groupe constitué de deux ou plusieurs de ces groupes et liaisons, et X, Y, T, l et k ayant les mêmes significations que celles définies dans la formule générale I, sont copolymérisés avec un ou plusieurs monomères présentant la moitié sensibilisateur représentée par la formule générale suivante :
CH_2= C(E) -Z-S
dans laquelle E et Z ont les mêmes significations que celles définies dans la formule générale VI et S représente la moitié sensibilisateur et facultativement un ou plusieurs autres monomères présentant une liaison éthyléniquement insaturée.
17. Procédé selon la revendication 15, dans lequel un ou plusieurs monomères présentant la moitié contenant un groupe carboxyle représentée par la formule générale VII suivante :
(HOCH_2CH_2)-N-Z-(Y)_l -X-(CH_2)_k-COOT (VII)
dans laquelle X, Y, T, l et k ont les mêmes significations que celles définies dans la formule générale I et Z représente un groupe de pontage comprenant une simple liaison sont copolymérisés avec un ou plusieurs monomères présentant la moitié sensibilisateur représentée par la formule générale VIII suivante :
(HOCH_2CH_2) -N-Z-S (VIII)
dans laquelle Z représente un groupe de pontage comprenant une liaison simple et S représente une moitié sensibilisateur.
18. Procédé selon la revendication 15, dans lequel un ou plusieurs monomères présentant une moitié contenant un groupe carboxyle de la formule VII et un ou plusieurs monomères présentant la moitié sensibilisateur de la formule VIII réagissent avec un ou plusieurs composés présentant des groupes fonctionnels de chlorure d'acide aux deux terminaisons de ceux-ci.